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EP4077255B1 - Procédé de préparation d'hydroquinones - Google Patents

Procédé de préparation d'hydroquinones Download PDF

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Publication number
EP4077255B1
EP4077255B1 EP20821235.7A EP20821235A EP4077255B1 EP 4077255 B1 EP4077255 B1 EP 4077255B1 EP 20821235 A EP20821235 A EP 20821235A EP 4077255 B1 EP4077255 B1 EP 4077255B1
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Prior art keywords
solvent
formula
process according
reduction
anyone
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German (de)
English (en)
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EP4077255A1 (fr
Inventor
Werner Bonrath
Thomas Netscher
Jonathan Alan Medlock
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DSM IP Assets BV
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DSM IP Assets BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring

Definitions

  • the present invention relates to the preparation of hydroquinones from the respective quinones.
  • hydroquinones are important intermediates. Particularly, methyl- or dimethyl- or trimethyl-hydroquinones are known as intermediates for tocopherol synthesis. Particularly important is the reduction of 2,3,5-trimethylquinone (TMQ) as 2,3,5-trimethylhydroquinone (TMHQ) is a well-known intermediate for ⁇ -tocopherol.
  • TMQ 2,3,5-trimethylquinone
  • TMHQ 2,3,5-trimethylhydroquinone
  • TMHQ TMHQ
  • DE 683 908 describes methanol and ethanol as solvent. These solvents, however, lead to autoxidation of TMHQ and undesired coloration and, hence, are considered as being unsuitable solvents for this reaction.
  • TMHQ TMHQ
  • the product of hydrogenation is precipitated and leads to incrustation which increase cost for maintenance of the reaction equipment as well as for the regeneration of the hydrogenation catalyst.
  • DE 1 940 386 solves this problem by using an aliphatic alcohol with 3 to 5 carbon atoms as solvent and using a temperature of 60 - 180°C.
  • EP 0 264 823 A1 propose other solvents such as ketones, organic acids, organic acid esters, ethers, cyclic ethers, and lactones as solvents for the hydrogenation of solvents.
  • solvents have deficiencies in view of environmental aspects, chemical stability towards acids and/or bases and toxicology or fire hazards.
  • DE 22 50 066 A1 discloses the reduction of 2,3,5-trimethylbenzoquone with hydrogen in the presence of a hydrogenation catalyst in a carbonic acid ester with 2 to 12 carbon atoms.
  • Cyclic alkyl carbonates are, somehow, still unusual solvents for chemical reactions, the more and more, however, these solvents are used due to excellent ecotoxicity and positive fire and working hazard properties. Finally, alkylene carbonates are attractive in view of cost.
  • alkylene carbonates which is well-known to those skilled in the art, are prone to hydrolysis.
  • the hydrolysis leads to formation of CO 2 and the respective alkanediol.
  • phenol and alkylene carbonates form different alkanediol ethers of the phenols.
  • the problem to be solved by the present invention is to reduce quinones of the formula (III) to hydroquinones of the formula (I) in a solvent which assures that the quinones of the formula (III) as well as the hydroquinones of the formula (I) remain dissolved and in which the formation of side products is mostly avoided.
  • the process according to claim 1 is surprisingly suited to solve this problem. It particularly has been found that no precipitation of the hydroquinone has been formed and that the alkylene carbonates of the formula (X) used as solvents does not decompose under the conditions of the reduction. Contrary to the expectation, no indication of any degradation of the solvent, such as formation of CO 2 or an increased amount of alkanediols or the respective alkanediol ether derivatives of the hydroquinones has been found.
  • the present invention relates to a process for the manufacturing the compound of the formula (I) by reduction of the compound of the formula (III)
  • C x-y -alkyl is an alkyl group comprising x to y carbon atoms, i.e., for example, a C 1-3 -alkyl group is an alkyl group comprising 1 to 3 carbon atoms.
  • the alkyl group can be linear or branched. For example -CH(CH 3 )-CH 2 -CH 3 is considered as a C 4 -alkyl group.
  • a "C x-y -alkane” accordingly corresponds to a linear or branched alkane comprising x to y carbon atoms.
  • inert means that under the conditions of the reaction said material does not undergo any chemical reaction.
  • R 1 , R 2 and R 3 independently represent preferably either H or a methyl group.
  • the compound of the formula (III) is reduced in the above process to the compound of the formula (I) by a reducing agent.
  • the reducing agent is molecular hydrogen.
  • the compound of the formula (III) is hydrogenated by molecular hydrogen in the presence of a metal catalyst.
  • the metal of the metal catalyst is preferably selected from the group consisting of Ni, Ir, Pd, Pt, Rh and Ru, particularly Pd or Pt, particularly a heterogeneous metal catalyst on a carrier or a support material.
  • the metal catalyst can be a catalyst comprising more than one of the mentioned metals.
  • the metal of the metal catalyst is palladium.
  • the metal catalyst is preferably a heterogeneous metal catalyst on a carrier or a support material.
  • Such carrier material is particularly a solid material having a high surface area, to which the metal is affixed.
  • the support may be inert or participate in the catalytic reactions.
  • Typical supports/carrier material include various kinds of carbon or an oxide of Si, Al, Ce, Ti or Zr, particularly of Al or Si, such as alumina or silica.
  • the preferred support/carrier material is carbon.
  • the preferred oxide is CeO 2 .
  • the oxide of Al is Al 2 O 3 and AlO(OH). Particularly preferred is Boehmite.
  • the surface area of the carrier is preferably in the range of 800 to 1500 m 2 /g, particularly of 1000 to 1200 m 2 /g.
  • the heterogeneous metal catalyst may also be affixed or immobilized on a surface of a larger object typically in form of a structured packing element which might be a part of the reactor in which the reduction takes place or an element which is inserted into said reactor.
  • the support material is, hence, preferably a structured packing element.
  • This structured packing element may be a dumped packing, a knit, an open-celled foam structure, preferably made of plastic, for example polyurethane or melamine resin, or ceramic, or a structured packing element, as already known in principle, i.e. by its geometric shape, from distillation and extraction technology.
  • structured packings in principle have a substantially smaller hydraulic diameter, frequently by a factor of from 2 to 10, than comparable internals in the field of distillation and extraction technology.
  • Useful structured packing elements are in particular metal fabric packings and wire fabric packings, for example of the design Montz A3, Sulzer BX, DX and EX.
  • structured packings made of other woven, knitted or felted materials are also possible.
  • Further useful structured packings are of flat or corrugated sheets, preferably without perforation, or other relatively large orifices, for example corresponding to the designs Montz BI or Sulzer Mellapak.
  • the structured packings made of expanded metal are also advantageous, for example structured packings of the type Montz BSH.
  • the metal catalyst is a palladium catalyst, particularly a palladium on carbon catalyst (Pd/C).
  • the catalytic metal loading (weight ratio metal/catalyst, i.e. the weight metal / weight (metal+carrier)) is typically between 1 to 20%, preferably between 4 and 11%, more preferably between 4 and 6% by weight.
  • the reducing agent is a transfer hydrogenation agent.
  • the compound of the formula (III) is transfer hydrogenated by a transfer hydrogenation agent to yield the compound of the formula (I).
  • Said transfer hydrogenation agent is preferably formic acid and/or a formic acid salt.
  • the reducing agent is a dithionite salt.
  • the reduction can be achieved with sodium dithionite in water according to the method as disclosed by K. Sato, Y. Fujima, A. Yamada Bull. Chem. Soc. Jap. 1968, 41, 442-444 .
  • the reducing agent is either molecular hydrogen or a transfer hydrogenation agent or a dithionite salt.
  • the substituent Y 1 is preferably H.
  • ethylene carbonate is a preferred solvent of the formula (X).
  • propylene carbonate is another preferred solvent of the formula (X).
  • butylene carbonate is another preferred solvent of the formula (X).
  • Ethylene carbonate and propylene carbonate are the most preferred solvents of the formula (X).
  • the reduction is performed in at least two solvents of the formula (X), particularly a binary or ternary mixture of ethylene carbonate and/or propylene carbonate and/or butylene carbonate, most preferably a binary mixture of ethylene carbonate and propylene carbonate. It is preferred that the ratio of ethylene carbonate to propylene carbonate is between 20:80 to 80:20, particularly 25:75 to 75:25.
  • the solvent of the formula is a carbonate solvent as commercialized by Huntsman under the trademark Jeffsol ® , particularly the blends of ethylene carbonate with propylene carbonate Jeffsol ® EC-75, Jeffsol ® EC-50 and Jeffsol ® EC-25.
  • the reduction is performed in a two-phase solvent mixture comprising at least one solvent ( A ) being of a solvent of the formula (X) and at least one solvent ( B ) which is not miscible with solvent of the formula (X) at room temperature in a volume ratio of ( A )/( B ) of between 1/50 and 50/1.
  • the solvent ( B ) which is not miscible with the solvent ( A ) of the formula (X) is preferably a hydrocarbon, more preferably an alkane, particularly a C 5-16 -alkane, most particularly a C 6-8 -alkane. Most preferably the solvent (B) is either hexane or heptane.
  • the catalyst can be easily removed from the reaction mixture.
  • Particularly useful for this separation are either filtration or extraction.
  • the process is also very advantageous in that on the one hand the compound of the formula (III) can be prepared in the solvent of the formula (X) and the condensation of the compound of the formula (I) with phytol or isophytol to yield tocopherol on the other hand can be performed in the solvent of the formula (X).
  • This is particularly advantageous as no change of solvent needs to be made during the whole process starting from (poly) alkylphenol to tocopherol.
  • Alkylene carbonates are very attractive solvents due to their excellent ecotoxicity and positive fire and working hazard properties as well as in view of cost.
  • the invention relates to the use of ethylene carbonate and/or propylene carbonate and/or butylene carbonate as a solvent for the reduction of 2,3,5-trimethyl-1,4-benzoquinone to 2,3,5-trimethylhydroquinone.
  • the present invention is further illustrated by the following experiments.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (14)

  1. Procédé pour la fabrication du composé de la formule (I) par réduction du composé de la formule (III)
    Figure imgb0009
    R1, R2 et R3 représentant indépendamment soit H, soit un groupe alkyle en C1-4, à la condition qu'au moins l'un des radicaux R1, R2 et R3 soit différent de H ; caractérisé en ce que la réduction est réalisée par un agent de réduction dans au moins un solvant de la formule (X)
    Figure imgb0010
     Y1 et Y2 représentant indépendamment l'un de l'autre soit H, soit un groupe méthyle ou éthyle ;
    ou dans un mélange de solvants biphasique comprenant au moins un solvant (A) qui est un solvant de la formule (X) et au moins un solvant (B) qui n'est pas miscible avec un solvant de la formule (X) à température ambiante en un rapport volumique de (A)/(B) compris entre 1/50 et 50/1.
  2. Procédé selon la revendication 1, caractérisé en ce que Y1 = Y2 = H.
  3. Procédé selon la revendication 1, caractérisé en ce que Y1 = H et Y2 = CH3.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la réduction est réalisée dans un mélange de solvants d'un solvant (A) qui est un solvant de la formule (X) et d'un solvant (B) qui est un hydrocarbure, préférablement un alcane, plus préférablement un alcane en C5-16, particulièrement un alcane en C6-8.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la réduction est réalisée dans un mélange de solvants d'au moins deux solvants de la formule (X), particulièrement dans un mélange de carbonate d'éthylène et de carbonate de propylène.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la réduction est réalisée en utilisant un agent de réduction qui est soit l'hydrogène moléculaire, soit un agent d'hydrogénation par transfert, soit un sel de dithionite.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la réduction est réalisée en utilisant un agent de réduction qui est l'hydrogène moléculaire en la présence d'un catalyseur métallique, le métal étant choisi dans le groupe constitué par Ni, Ir, Pd, Pt, Rh et Ru, particulièrement Pd ou Pt, particulièrement un catalyseur métallique hétérogène sur un support ou un matériau de support.
  8. Procédé selon la revendication 7, caractérisé en ce que le support est un carbone ou un oxyde de Si, Al, Ce, Ti ou Zr, particulièrement de Al ou Si, préférablement un carbone.
  9. Procédé selon la revendication 7 ou 8, caractérisé en ce que le catalyseur est Pd sur carbone.
  10. Procédé selon l'une quelconque des revendications précédentes 7 à 9, caractérisé en ce que l'aire de surface du support est dans la plage de 800 à 1 500 m2/g, particulièrement de 1 000 à 1 200 m2/g.
  11. Procédé selon la revendication 7, caractérisé en ce que le matériau de support est un élément de remplissage structuré.
  12. Procédé selon l'une quelconque des revendications 7 à 11, caractérisé en ce que le rapport du poids du métal, particulièrement de Pd ou Pt, sur le poids du catalyseur est compris entre 1 et 20 %, préférablement entre 4 et 11 %, plus préférablement entre 4 et 6 % en poids.
  13. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que R1 = R2 = R3 = CH3.
  14. Utilisation de carbonate d'éthylène et/ou de carbonate de propylène et/ou de carbonate de butylène en tant que solvant pour la réduction de 2,3,5-triméthyl-1,4-benzoquinone en 2,3,5-triméthylhydroquinone.
EP20821235.7A 2019-12-19 2020-12-14 Procédé de préparation d'hydroquinones Active EP4077255B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19217785 2019-12-19
PCT/EP2020/085940 WO2021122436A1 (fr) 2019-12-19 2020-12-14 Procédé pour la préparation d'hydroquinones

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EP4077255A1 EP4077255A1 (fr) 2022-10-26
EP4077255B1 true EP4077255B1 (fr) 2024-01-31

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CN (1) CN114829327B (fr)
ES (1) ES2978483T3 (fr)
WO (1) WO2021122436A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4077259B1 (fr) * 2019-12-19 2024-01-31 DSM IP Assets B.V. Formation de 2,3,5-triméthylhydroquinone à partir de 2,3,6-triméthylphénol

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE683908C (de) 1938-05-05 1939-11-18 Merck Chem Fab E Verfahren zur Herstellung von Trimethylhydrochinon
BE754559A (fr) 1969-08-08 1971-02-08 Basf Ag Procede pour la preparation de trimethylhydroquinone
DE2250066C3 (de) * 1971-11-05 1979-04-05 Kuraray Co., Ltd., Kurashiki, Okayama (Japan) Verfahren zur Herstellung von 233-Trimethylhydrochinon durch katalytische Hydrierung von 233-Trimethylbenzochinon
JPH07107003B2 (ja) 1986-10-16 1995-11-15 三菱瓦斯化学株式会社 ２，３，５−トリメチルハイドロキノンの製造方法
DE10017494A1 (de) * 2000-04-07 2001-10-11 Degussa Verfahren zur Herstellung von Trimethylhydrochinon-Diacetat und Trimethylhydrochinon
US20030060383A1 (en) 2001-09-17 2003-03-27 Huntsman Petrochemical Corporation Methods for stabilizing aqueous alkylene carbonate solutions
US7361781B2 (en) * 2003-11-07 2008-04-22 Dsm Ip Assets B.V. Process for the preparation of 2,3,5-trimethylhydroquinone diacylates
JPWO2006051747A1 (ja) * 2004-11-10 2008-05-29 イハラケミカル工業株式会社 ２−ベンジルフェノール化合物の製造方法
JP2007045744A (ja) * 2005-08-10 2007-02-22 Ihara Chem Ind Co Ltd ２−ベンジルフェノール類の製造法
JP5026739B2 (ja) * 2006-06-03 2012-09-19 イハラケミカル工業株式会社 β−ナフトール類の製造方法
EP4077259B1 (fr) * 2019-12-19 2024-01-31 DSM IP Assets B.V. Formation de 2,3,5-triméthylhydroquinone à partir de 2,3,6-triméthylphénol
CN114901650B (zh) * 2019-12-19 2024-09-03 帝斯曼知识产权资产管理有限公司 由2,3,6-三甲基苯酚形成α-生育酚

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ES2978483T3 (es) 2024-09-13
CN114829327B (zh) 2024-11-19
EP4077255A1 (fr) 2022-10-26
CN114829327A (zh) 2022-07-29
WO2021122436A1 (fr) 2021-06-24

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